DOCSLIB.ORG

Synthesis and Reactions of Substituted Bipyridines

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Synthesis and Reactions of Substituted Bipyridines Syntheses and Reactions of Substituted Bipyridines By: Hazarry bin Haji Ali Ahmad 00B2140 Supervisors: Dr. F. Wimmer Dr. Chan Chin Mei Project Report submitted to Department of Chemistry University of Brunei Darussalam in partial fulfillment for Bachelor of Science Education degree. Table of Contents Page No. Acknowledgments ……………………………………………………… 2 Abstract ……………………………………………………… 3 List of abbreviations ……………………………………………………… 4 1. Introduction ……………………………………………………… 5 - 12 1.1 Aims of project ……………………………………………… 12 2. Experimental ……………………………………………………… 13 - 24 2.1 Preparation of substituted bipyridine ……………………… 13 2.2 Synthesis of Complexes ……………………………………… 19 3. Results and Discussions ……………………………………………… 25 - 53 3.1 Preparation and properties of substituted bipyridine ……… 25 3.2 Syntheses and properties of Complexes ……………………… 37 3.3 Interpretation of the IR spectra of complexes ……………… 43 3.4 Electronic spectroscopy of the complexes ……………… 47 3.5 Interpretation of H-NMR spectra of complexes ……………… 52 4. Conclusions ……………………………………………………… 54 - 55 5. Appendices ……………………………………………………… 56 - 91 Appendix A: IR Spectra of substituted 2,2’-bipyridines ……… 57 Appendix B: IR Spectra of complexes ……………………… 66 Appendix C: Electronic spectra of complexes ……………… 80 Appendix D: 1H-NMR spectra of complexes ……………… 87 References ……………………………………………………… 92 - 94 Front cover: 3-dimensional structure of substituted bipyridine (2,2’-bipyridyl-3,3’- carbinol) using Advanced Chemistry Development Inc’s ACD/3D Viewer. 1 ACKNOWLEDMENTS Firstly, I wish to convey my special acknowledgment to both of my supervisors, Dr. F. Wimmer and Dr. Chan Chin Mei, for your guidance, support and advice throughout the research. Your valuable time and concerns are highly appreciated. Especially, I am indebted for your encouragement and help during the last, tense times preparing the papers and the thesis. The study was carried out in the Department of Chemistry at the University of Brunei Darussalam in July – November 2003. Although in my own opinion it was quite a short period of research, during my research I found that the study is very motivating. I also wish to thank all the staff in the Department of Chemistry. My sincere thanks are also due to my friends and colleagues for all of your support and providing a warm and supporting atmosphere in the Laboratory. Most importantly I wish to thank my beloved parents and families for their support during my studies. Hazarry Haji Ali Ahmad November 2003 2 Abstract Synthesis of the substituted bipyridine2,2’-bipyridyl-3,3’-dicarbinol, bipyridine was attempted from 1,10-phenantroline. Six different bipyridine ligands (2,2’-biquinoline; 5-nitro-1,10-phenantroline; neocuproin, bathophenantroline and 6,7-dimethyl-2,3- di(2-pyridyl)quinoxaline) which cover a wide range of electronic and steric properties were successfully complexed with Mo(CO)6. The properties of the complexes were studied and characterized by infrared and proton nuclear magnetic resonance spectroscopy, and by electronic spectroscopy to study their solvatochromic properties. 3 List of abbreviations BPhen Bathophenantroline Bpy Bipyridine N N BiQ 2,2’-Biquinoline N N DCMB 3,3’-Dicarbomethoxy-2,2’-bipyridine Bathophenantroline 2,2'-Biquinoline DDPQxn 6,7-dimethyl-2,3-di(2-pyridyl)quinoxaline DCMBiQ 4,4’-dicarbomethoxy-2,2’-biquinoline N H3COOC DMF Dimethylformamide H3COOC N EtOH Ethanol 3,3'-Dicarbomethoxy-bipyridine IR Infrared N N UV Ultraviolet N N MeOH Methanol 6,7-Dimethyl-2,3-di(2-pyridyl)quinoxaline MLCT Metal to ligand charge transfer H3COOC NPhen 5-nitro-1,10-phenantroline N NeoC Neocuproin N Rf Refractive index H3COOC 4,4'-dicarbomethoxy-biquinoline t-BuOH tert-Butyl alcohol (2-Methyl-2-propanol) CH3 TLC Thin-layer chromatography N N THF Tetrahydrofuran O2N N N TMNO Trimethylamine-N-oxide CH3 5-Nitro-1,10-phenanthroline Neocuproin 4 1. Introduction Pure 2,2’-bipyridine (Equation 1) was first synthesized in the late 19th century by distillation of copper picolinate. A more convenient synthesis was eventually achieved when Raney-Nickel alloy was used as a catalyst 25. Since the preparation of the first 2,2’-bipyridine, the derivatives of bipyridine have been widely employed in complexation experiments. N CO2- ∆ N N 2,2'-Bipyridine Equation 1. Synthesis of 2,2’-Bipyridine Transition metals in low oxidation states are able to form complexes with many unsaturated organic ligands. The interactions between the ligands and the metal depend on the orientation of the orbitals with respect to each other. According to their interactions, ligands are classified into three types: σ-donor ligands, π-donor ligands and π-acceptor ligands 2. So, 2,2’-bipyridine is both a σ-donor and a π-acceptor ligand. The lone electron pair of nitrogen can form a σ-bond with the central atom, while the aromatic system can take part in back-bonding. These will stabilize metal ions, especially transition metal ions in low oxidation states. 5 In addition, ligands with two or more donor atoms are able to form a chelate ring with metal atoms. The diimine part of the bipyridine delocalizes the electrons in the chelate ring. This ability to coordinate has led to an extremely rich chemistry and constitutes the basis of many important industrial catalytic processes. For example, complexes of methyl substituted bipyridine as catalyst in atom transfer radical polymerization of styrene and acrylates 17. 2,2’-Bipyridines are of special interest as complex ligands in coordination and supramolecular chemistry. Their prolonged, luminescent, charge transfer state enables them to be used as sensitizers in photochemistry5. Bipyridine complexes are also 4 significant in catalytic studies in the reduction of CO2 and the hydroformylation of olefins 15. It is essential in coordination chemistry to understand how ligands are bonded to metal atoms. 2,2’-bipyridine is a versatile chelating agent which binds to most metal ions. The electronic properties of bipyridine can be tailored by varying the substituents on the parent ligand and as a result this will modify the properties of the metal complexes7. In one part of this study, alcohol functional groups were aimed to be introduced at position 3,3’ of 2,2’-bipyridine which would change the electronic and steric properties of the bipyridine. The proposed synthesis is shown in Scheme 1. The starting material is phenanthroline. Oxidation of 1,10 phenanthroline yields binicotinic acid (Product A), the carboxylic acid substituents at 3,3’-position of the 2,2’-bipyridine9. The next step was to convert the acid into the ester (Product B), 3,3’- 6 dicarbomethoxy-2,2’-bipyridyl (DCMB). Alcohols can be synthesized from esters with Grignard reagent (Product C) or by reduction with sodium borohydride in mixed solvent10 (Product D). Group VIA of the transition metals i.e. Cr(CO)6, Mo(CO)6 and W(CO)6 were purposely being used in this study as they are neutral and stable metal carbonyls1 having octahedral coordination. CO can be replaced by an isoelectronic equivalent having two electrons for example H- and a ligand having a lone pair of electrons such as nitrogen. A study of these hexacarbonyls using infrared and Raman spectra determined the mean dissociation energies for the loss of the first CO in order relative 7 to each other: Cr(CO)6 < Mo(CO)6 > W(CO)6 . Hence, generally, we would expect molybdenum hexacarbonyl being more reactive than chromium and tungsten. 7 Product A Oxidation O N HO N 1. KMnO4, NaOH, H2O + 2. H3O N HO N O 1,10-Phenanthroline 2,2'-Bipyridine-3,3'-dicarboxylic acid (Binicotinic acid) Product C Esterification + MeOH, H3O Grignard reaction OH 1. 4 CH MgBr, dry ether H C N 3 3 + 2. H3O H3C H C 3 Product B H3C N OH O O N H3C H3C O N Product D O 3,3'-dicarbomethoxy-bipyridine HO N (DCMB) Reduction HO N NaBH4, tert-BuOH/MeOH 2,2'-bipyridyl-3,3'-carbinol Scheme 1: Proposed synthetic route for the preparation of substituted 3,3’- alcohol functional group of bipyridine ligand. 8 Infrared spectroscopy When CO coordinates to a metal center, electron density from a lone-pair on the carbon is donated to the metal, while at the same time the π*-orbitals of the ligand receives electron density from the metal, thereby strengthening the metal-ligand bond. This is known as synergistic bonding1. CO is particularly powerful in withdrawing electron density from the metal in this way, i.e. it is a good π-acceptor. Since the C-O stretching frequency is easily observed in the IR spectrum, the position of this band is a sensitive probe for the electron density of the metal center 3 as well as the structural information6. The number of infrared bands depends on the molecular symmetry of the metal carbonyl complexes hence its geometry. For a vibration modes to be infrared active there must be a change in the dipole moment of the molecule. Because not all vibrations result in a change in dipole moment, this type of vibration will be invisible 3 in the infrared spectrum . For terminal M-CO, the approximate range for Vco in neutral complexes ranges between 1850 – 2120 cm-1. Predicting the number of carbonyl bands of complexes having more than two carbonyls involved the use of Group theory8. From the infrared spectrum of metal carbonyl complex, one may be able to decide among several alternatives geometries for a compound. For a complex having octahedral coordination, the number of bands expected for a variety of CO complexes is given in Table 1. Hence by inferring the number of bands in the infrared spectra of the complex can verify whether the reaction has completed. 9 Table 1: Infrared active carbonyl stretching bands. Number of CO stretching Geometry Carbonyls bands L OC CO 4 M 1 OC CO L L OC L 4 M 4 OC CO CO L OC CO 5 M 3 OC CO CO CO OC CO 6 M 1 OC CO CO * L is a ligand.
Load more

Recommended publications
  • Infrared Studies of Group Vib Metal Carbonyl Derivatives
    INFRARED STUDIES OF GROUP VIB METAL CARBONYL DERIVATIVES APPROVED t Graduate CommitteeJ irmci Maj6r Prenfessor Committee Member ciu.// Committee Member mmittee Member Director of the Department of Chemistry Dean df the Graduate School Brown, Richard A.. Infrared Studies of Group VIB Metal Carbonvl Derivatives. Doctor of Philosophy (Chemistry), August, 1971, 80 pp., 17 tables, 17 figures, bibliography, 66 titles. The infrared spectra in the carbonyl stretching region and metal-carbon stretching region have been obtained for sixty-one derivatives of M(C0)g (M * Cr, Mo, or W). The CO and MC stretch- ing frequencies have been used to help resolve the inconsistencies and discrepancies on bonding in octahedral metal carbonyls found in the literature. Thirty-seven monosubstituted complexes of the general formula LM(C0)5 (L SS a monodentate ligand containing a N, P, As, Sb, Bi, 0, or S donor atom) were prepared by thermal, photolytic, or re- placement reactions in various organic solvents. Twenty-six di- substituted complexes of the general formula cls-(bid)M(CO)^ (bid = a bidentate ligand containing N, P, As, or S donor atoms) were also prepared. Plots of the A^ and E mode carbonyl stretching frequencies and the k^ and CO force constants of ten (amine)W(C0)^ com- plexes vs. the pK of the amine were made. No correlations be- tween the trans -CO parameters [t>(C0) A^ and k^] and the pK& could be identified. Consequently, it was concluded that the isotropic inductive effect, which transmits electronic charge through the central metal sigma system, has no observable effect on the CO stretching frequencies.
    [Show full text]
  • Relative Chalcogen Donor Properties in Transition Metal Complexes. Eugene D
    Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1971 Relative Chalcogen Donor Properties in Transition Metal Complexes. Eugene D. Schermer Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Schermer, Eugene D., "Relative Chalcogen Donor Properties in Transition Metal Complexes." (1971). LSU Historical Dissertations and Theses. 1949. https://digitalcommons.lsu.edu/gradschool_disstheses/1949 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. 71-20,621 SCHERMER, Eugene D., 1934- RELATIVE CHALCOGEN DONOR PROPERTIES IN TRANSITION METAL COMPLEXES. The Louisiana State University and Agricultural and Mechanical College, Ph.D., 1971 Chemistry, inorganic University Microfilms, A XEROXCompany, Ann Arbor, Michigan THIS DISSERTATION HAS BEEN MICROFILMED EXACTLY AS RECEIVED Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. RELATIVE CHALCOGEN DONOR PROPERTIES IN TRANSITION METAL COMPLEXES A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Eugene D. Schemer B.A., Eastern Washington State College, 1958 M.S., Oregon State University, 1Q62 January, 197! Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGEMENT The author wishes to express his sincere gratitude to Professor William H. Baddley, under whose direction this work was produced.
    [Show full text]
  • 91P4D148-1-31 T ORGANOMETALLIC COMPOUNDS of BORON and SOME TRANSITION METALS a Thesis Submitted for the Degree of Doctor Of
    91P4D148-1-31T ORGANOMETALLIC COMPOUNDS OF BORON AND SOME TRANSITION METALS A Thesis submitted for the Degree of Doctor of Philosphy in the University of London by APAR SINGH Imperial College of Science and Technology, London, SOV.7. December, 1959. DEDICAT7D TO MY PROF7,SSOR. ABSTRACT. Part I describes the preparation and properties of tristr:Lalkyl- silyl esters of boron. The most convenient method was, howeve:7, by the silanolysis of trisdiethylamino boron. Bistriethylsilyl phenyl boronate [(2t3Si0)2BPh)] and triethylsilyldiphenyl borinate [(Tqt3Si0BPh21 have been prepared. These compounds undergo slow hydrolysis and rapid dealkylation with halogen acids, and are thermally very stable. The trisalkylsilyl metaborates have been formed :from bori oxide and the corresponding orthoborates. They are trimeric (cryoscopic measurement) and possess cyclic boroxole structure, which is supported by the presence of a doublet at 720 and 735 cm. in the infrared structure recently assigned to the out-of-plane vibration of boroxole skeleton. Part II describes a number of substituted binuclear cyclopentadienyl carbonyls of molybdenum, tungsten and iron, which have been made by the direct interaction of the metal carbonyls with fulvones. The corres- ponding mononuclear iodides and some alkyl derivatives have been obtained. n-Cyclopentadianyl molybdenum 7-cyclopentadienyl tungsten hexacarbonyl, 7t-05115Mo(C0)6W.n-05H5, is the first reported complex compound with a metal-metal bond between different transition metal atoms. Abstract (continued). Triphenylphosphonium cyclopentadienylide metal complexes of molybdenum, tungsten, chromium and iron have been prepared by the direct interaction of the metal carbonyl with triphenylphosphonium cyclopenta- dienylide in which the five-membered carbocyclic ring (cyclopentadienyl ring) has a sextet of electrons and acts as a six-electron donor ligand comparable to aromatic hydrocarbons.
    [Show full text]
  • United States Patent Office Patented Apr
    3,381,023 United States Patent Office Patented Apr. 30, 1968 1. 2 Furthermore, the isolation procedures for separating the 3,381,023 resulting compounds are simplified by the process of this PREPARATION OF AROMATIC GROUP VI-B METAL TRICARBONYS invention, as a minimum of unreacted starting materials Mark Crosby Whiting, Oxford, England, assignor to and side products are present in the final composition. In Ethyl Corporation, New York, N.Y., a corpora addition, Superior yields are obtained. For example, tion of Virginia O-cresyl methylether chromium tricarbonyl was prepared No Drawing. Filed Mar. 10, 1958, Ser. No. 720,083 in 99 percent yield by the process of this invention. Yields 31 Claims. (Ci. 260-429) of this order of magnitude have not heretofore been pos sible. This invention relates to a process for the preparation The temperatures employed in the process of this inven of organometallic compounds and more particularly the O tion may vary over a wide range. In general, tempera preparation of aromatic Group VI-B transition metal tures of from about 100° C. to 300° C. are employed. carbonyl compounds. However, a preferred range of temperature is from Recently a method for the preparation of aromatic 150 C. to 225 C. as the reaction in this temperature chromium tricarbonyl compounds has been proposed, 5 range leads to a high yield of products with a minimum which method comprises the equilibration, in an aromatic of undesirable side reactions. Solvent of a di-aromatic chromium compound with chro The aromatic compound which is a reactant in the mium hexacarbonyl and which employs a reaction time process of this invention can be selected from a wide of 12 hours under pressure at temperature in excess of range of aromatic organic compounds including mono 200 C.
    [Show full text]
  • Photochemical Substitution Reactions of Some Transition Metal Carbonyl Complexes
    DOKUZ EYLUL UNIVERSITY GRADUATE SCHOOL OF NATURAL AND APPLIED SCIENCES PHOTOCHEMICAL SUBSTITUTION REACTIONS OF SOME TRANSITION METAL CARBONYL COMPLEXES by Pelin KÖSE June, 2008 İZMİR PHOTOCHEMICAL SUBSTITUTION REACTIONS OF SOME TRANSITION METAL CARBONYL COMPLEXES A Thesis Submitted to the Graduate School of Natural and Applied Sciences of Dokuz Eylül University In Partial Fulfillment of the Requirements for the Degree of Master of Science in Chemistry by Pelin KÖSE June, 2008 İZMİR M.Sc THESIS EXAMINATION RESULT FORM We have read the thesis entitled “PHOTOCHEMICAL SUBTITUTION REACTIONS OF SOME TRANSITION METAL CARBONYL COMPLEXES” completed by PELİN KÖSE under supervision of ASSOC. PROF. DR. ELİF SUBAŞI and we certify that in our opinion it is fully adequate, in scope and in quality , as a thesis fort he degree of Master of Science ASSOC. PROF. DR. ELİF SUBAŞI Supervisor (Jury Member) (Jury Member) Prof.Dr. Cahit HELVACI Director Graduate School of Natural and Applied Scineces ii ACKNOWLEDGMENTS First of all, I would like to thank Assoc. Prof. Dr. Elif SUBASI for her constant supervision, her valuable advise, guidance and encouragement. I also thank to Research Assistant Senem KARAHAN for her help in our study. I am grateful to Research foundation of Dokuz Eylul University for supporting the 2005.KB.FEN.019; 2006.KB.FEN.020 numbered projects. Finally, I would like to thank my mother, Leyla KOSEHALILOGLU and the other members of my family for their great encouragement. Pelin KÖSE iii PHOTOCHEMICAL SUBSTITUTION REACTIONS OF SOME TRANSITION METAL CARBONYL COMPLEXES ABSTRACT Transition metal carbonyl complexes especially VIB metal carbonyls are the oldest classes of organometallic chemistry.
    [Show full text]
  • Palladium-Catalyzed Molybdenum Hexacarbonyl-Mediated Gas-Free Carbonylative Reactions
    SYNLETT0936-52141437-2096 © Georg Thieme Verlag Stuttgart · New York 2019, 30, 141–155 account 141 en Syn lett L. Åkerbladh et al. Account Palladium-Catalyzed Molybdenum Hexacarbonyl-Mediated Gas-Free Carbonylative Reactions Linda Åkerbladh Luke R. Odell* Mats Larhed* 0000-0001-6258-0635 Department of Medicinal Chemistry, Organic Pharmaceutical Chemistry, BMC, Uppsala University, Box 574, 75123 Uppsala, Sweden [email protected] [email protected] Received: 08.08.2018 plex examples of carbonylative processes and new technol- Accepted after revision: 03.09.2018 ogies such as the use of two-chamber systems for lab-scale Published online: 02.10.2018 DOI: 10.1055/s-0037-1610294; Art ID: st-2018-a0502-a synthesis and multicomponent reactions (MCRs). High- lighted methodologies were to a large extent selected from Abstract This account summarizes Pd(0)-catalyzed Mo(CO)6-mediat- the authors’ own laboratories. ed gas-free carbonylative reactions published in the period October In the late 1930s, hydroformylation with syngas (the Ro- 2011 to May 2018. Presented reactions include inter- and intramolecu- 2 lar carbonylations, carbonylative cross-couplings, and carbonylative elen reaction) and hydrocarboxylation with carbon mon- 3 multicomponent reactions using Mo(CO)6 as a solid source of CO. The oxide and water (the Reppe reaction) were discovered. presented methodologies were developed mainly for small-scale appli- However, the finding by Heck and co-workers in 1974 that cations, avoiding the problematic use of gaseous CO in a standard labo- organohalides could be carbonylatively coupled with ali- ratory. In most cases, the reported Mo(CO)6-mediated carbonylations were conducted in sealed vials or by using two-chamber solutions.
    [Show full text]
  • Synthesis of New Chiral 2,2′-Bipyridyl-Type Ligands, Their
    Organometallics 2001, 20, 673-690 673 Synthesis of New Chiral 2,2′-Bipyridyl-Type Ligands, Their Coordination to Molybdenum(0), Copper(II), and Palladium(II), and Application in Asymmetric Allylic Substitution, Allylic Oxidation, and Cyclopropanation Andrei V. Malkov,†,‡,§ Ian R. Baxendale,‡,¶ Marco Bella,†,⊥ Vratislav Langer,# John Fawcett,‡ David R. Russell,‡ Darren J. Mansfield,∇ Marian Valko,4 and Pavel Kocˇovsky´*,†,‡,§ Department of Chemistry, University of Glasgow, Glasgow G12 8QQ, U.K., Department of Chemistry, University of Leicester, Leicester LE1 7RH, U.K., Department of Inorganic Environmental Chemistry, Chalmers University of Technology, 41296 Go¨teborg, Sweden, Aventis CropScience UK Ltd, Chesterford Park, Saffron Walden, Essex, CB10 1XL, U.K., and Department of Physical Chemistry, Slovak Technical University, SK-812 37 Bratislava, Slovakia Received October 3, 2000 A series of chiral bipyridine-type ligands 5-12 has been synthesized via a de novo construction of the pyridine nucleus. The chiral moieties of the ligands originate from the monoterpene realm, namely, pinocarvone (13 f 6, 7, and 9), myrtenal (18 f 5), nopinone (21 f 8 and 10), and menthone (28 f 11 and 12); the first three precursors can be obtained in one step from â- and R-pinene, respectively. Complexes of these ligands with molybdenum(0) (38-40) and copper(II) (41) have been characterized by single-crystal X-ray crystallography. While complex 38 exhibits polymorphism (monoclinic and tetragonal forms crystallize from the same batch), 41 is characterized by a tetrahedrally distorted geometry of the metal coordination. The Mo and Pd complexes exhibit modest asymmetric induction in allylic substitution (43 f 44), and the Cu(I) counterpart of 41, derived from 10 (PINDY) and Cu(OTf)2, shows promising enantioselectivity (49-75% ee) and reaction rate (g30 min at room temperature) in allylic oxidation of cyclic olefins (47 f 48).
    [Show full text]
  • Download (1830Kb)
    SYNTHESIS AND CHARACTERIZATION OF ORGANOTUNGSTEN COMPLEX WITH MIXED P/S LIGAND By TEOH LING WEI A project submitted to the Department of Chemical Science Faculty of Science Universiti Tunku Abdul Rahman in partial fulfilment of the requirement for the degree of Bachelor of Science (Hons) Chemistry Oct 2015 ABSTRACT The reaction is carried out between equimolar ratio of tungsten tricarbonyl complex, (mes)W(CO)3 (1) and mixed P/S ligand, P(o-C6H4SCH3)2Ph, whereby they are refluxed in toluene for 18 hours under nitrogen gas flow. The reaction had led to the isolation of a chelate complex with tridentate bonding through P and S atoms, {P(o-C6H4SCH3)2Ph}W(CO)3 (2), with a percentage yield of 68%. The product is purified through column chromatography and gives light yellow crystalline solids. Complex is characterized by IR spectroscopy, 1H-, 13C-, and 31P- NMR spectroscopy. II ABSTRAK Tindakbalas antara (mes)W(CO)3 (1) dengan ligan P(o-C6H4SCH3)2Ph dalam nisbah setara, telah direflukskan dalam toluena selama 18 jam di bawah aliran gas nitrogen. Tindakbalas ini telah menghasilkan komplex kelat melalui ikatan dengan atom P and S, {P(o-C6H4SCH3)2Ph}W(CO)3 (2), dan mempunyai hasil peratusan sebanyak 68%. Produk ini akan ditukarkan menggunakan kromatografi turus dan memberikan pepejal berwarna kuning muda yang mempunyai ciri-ciri habur. Spektroskopi IR, 1H-, 13C-, dan 31P- RMN akan dijalankan ke atas produk ini untuk menentukan ciri-cirinya. III ACKNOWLEDGEMENT Firstly, I would like to take this opportunity to thank my supervisor, Dr. Ooi Mei Lee, who gave me a lot of help, advice and guidance on the research.
    [Show full text]
  • New Promoters for the Molybdenum Hexacarbonyl- Mediated Pauson–Khand Reaction
    General Papers ARKIVOC 2007 (xv) 127-141 New promoters for the molybdenum hexacarbonyl- mediated Pauson–Khand reaction Alexandre F. Trindade, Željko Petrovski,* and Carlos A. M. Afonso* CQFM, Departamento de Engenharia Química e Biológica, Instituto Superior Técnico, Complexo I, Av. Rovisco Pais, 1049-001 Lisboa, Portugal E-mail: [email protected] and [email protected] Abstract A systematic study of new additives for the stoichiometric molybdenum hexacarbonyl- mediated Pauson–Khand reaction resulted in the discovery of several active compounds such as tetra- substituted thioureas, ester and amide derivatives of phosphoric acid, quaternary ammonium bromides and phosphine oxides. Tributylphosphine oxide (TBPO) was the most efficient additive providing PK products in moderate to good yields. Some experimental evidences were found which support a non-oxidative Mo(CO)6 activation by TBPO. Keywords: Pauson–Khand, molybdenum hexacarbonyl, additives, phosphine oxide, thiourea, cyclopentenone Introduction Since its discovery1 in the early 1970s, the Pauson–Khand reaction (PKR) — originally mediated by cobalt and later found to proceed in the presence of other metal complexes (Rh, Ir, Ti, Zr, Fe, Ru, Cr, Mo, W, Ni, etc.) — has received great attention due to its potential application in complex molecules synthesis.2 The reaction can proceed in the presence of a stoichiometric amount of metal carbonyl (source of carbon monoxide) or catalytically under a CO gas atmosphere, or alternatively with compounds that can form such metal carbonyls. Most of the references related to the PKR that have appeared recently in the literature reflect an increasing interest for the development of novel transition metal catalysts and methods 3–9 for PKR and their application in organic synthesis.10–12 The first example of stoichiometric molybdenum mediated PKR was reported in 1992 by Hanaoka et al.
    [Show full text]
  • Chemelectrochem Supporting Information
    ChemElectroChem Supporting Information Electrochemically Driven Reduction of Carbon Dioxide Mediated by Mono-Reduced Mo-Diimine Tetracarbonyl Complexes: Electrochemical, Spectroelectrochemical and Theoretical Studies Carlos Garcia Bellido, Lucía Álvarez-Miguel, Daniel Miguel, Noémie Lalaoui, Nolwenn Cabon, Frédéric Gloaguen,* and Nicolas Le Poul* Wiley VCH Dienstag, 25.05.2021 2110 / 205453 [S. 1911/1911] 1 Contents 1. Synthesis and spectroscopic characterization of complexes 1-3…………………………S2 2. X-ray diffraction data…………………………………………………………………………...S7 3. UV-Vis spectroelectrochemistry………………………………………………………………S8 4. NIR-spectroelectrochemistry…………………………………………………………………S10 5. IR-spectroelectrochemistry …………………………………………………………………..S12 6. IR spectroscopy of chemically mono-reduced species and related coumpounds……...S14 7. Electrochemistry…………………………………………………………………………….…S16 8. CV simulations…………………………………………………………………………………S21 9. DFT calculations……………………………………………………………………………….S23 10. References……………………………………………………………………………………S28 S1 1. Synthesis and spectroscopic characterization of complexes 1-3 [1] Complexes 1-3 were synthesized according to reported procedures. As shown in Scheme S1, the general procedure consists of mixing [Mo(CO)6] with one equivalent of diimine ligand (bpy, phen or py-indz) in toluene under argon. The mixture is reacted under reflux. A colored (1: orange-red, 2: red; 3: yellow) precipitate is formed (see below) and washed with a 1:1 tol- uene/petroleum ether (15 mL) cold mixture. Scheme S1. Synthetic pathway for complexes 1-3 Tetracarbonyl(2,2´-bipyridine)molybdenum(0) (Complex 1) Molybdenum hexacarbonyl (0.69 g, 2.63 mmol) and 2,2´-bipyridine (0.41 g, 2.63 mmol) were refluxed in toluene for 90 minutes in dark conditions. The solution color changed from strong purple to red, forming a precipitate that was filtered and washed with cold toluene and diethyl ether, yielding an orange-red powder.
    [Show full text]
  • In Situ Generation of Molybdenum-Based Catalyst For
    In Situ Generation of Molybdenum-Based Catalyst for Alkyne Metathesis: Further Developments and Mechanistic Insights Joaquin Geng Lopez, Maciej Zaranek, Piotr Pawluc, Régis M. Gauvin, André Mortreux To cite this version: Joaquin Geng Lopez, Maciej Zaranek, Piotr Pawluc, Régis M. Gauvin, André Mortreux. In Situ Generation of Molybdenum-Based Catalyst for Alkyne Metathesis: Further Developments and Mech- anistic Insights. Oil & Gas Science and Technology - Revue d’IFP Energies nouvelles, Institut Français du Pétrole, 2016, 71 (2), pp.20. 10.2516/ogst/2015046. hal-01707485 HAL Id: hal-01707485 https://hal.archives-ouvertes.fr/hal-01707485 Submitted on 12 Feb 2018 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Oil & Gas Science and Technology – Rev. IFP Energies nouvelles (2016) 71,20 Ó J. Geng Lopez et al., published by IFP Energies nouvelles, 2016 DOI: 10.2516/ogst/2015046 Dossier Special Issue in Tribute to Yves Chauvin Numéro spécial en hommage à Yves Chauvin In Situ Generation of Molybdenum-Based Catalyst for Alkyne Metathesis: Further Developments and Mechanistic Insights Joaquin Geng Lopez1, Maciej Zaranek2, Piotr Pawluc1,2, Régis M. Gauvin1 and André Mortreux1* 1 Univ. Lille, CNRS, Centrale Lille, ENSCL, Univ.
    [Show full text]
  • Metal Carbonyl Complexes of Polycyclic Phosphite Esters David George Hendricker Iowa State University
    Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1965 Metal carbonyl complexes of polycyclic phosphite esters David George Hendricker Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Inorganic Chemistry Commons Recommended Citation Hendricker, David George, "Metal carbonyl complexes of polycyclic phosphite esters " (1965). Retrospective Theses and Dissertations. 3298. https://lib.dr.iastate.edu/rtd/3298 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. This dissertation has been nucroiihned• i-, J exactly.1 as received. 66-2989 HENDRICKER, David George, 1938- METAL CARBONYL COMPLEXES OF POLY- CYCLIC PHOSPHITE ESTERS. Iowa State University of Science and Technology Ph.D., 1965 Chemistry, inorganic University Microfilms, Inc., Ann Arbor, Michigan METAL CARBONYL COMPLEXES OF POLYCYCLIC PHOSPHITE ESTERS by David George Hendricker À Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of The Requirements for the Degree of DOCTOR OF PHILOSOPHY Major Subject: Inorganic Chemistry Approved; Signature was redacted for privacy. Charge of Major Work Signature was redacted for privacy. Head or Major Department Signature was redacted for privacy. D6 te College Iowa State University Of Science and Technology Ames, Iowa 1965 ii TABLE OF CONTENTS Page INTRODUCTION 1 EXPERIMENTAL 52 DISCUSSION 83 SUMMARY 136 SUGGESTIONS FOR FUTURE WORK 139 BIBLIOGRAPHY 142 ACKNO^EDGMENT 154 VITA 156 iii LIST OF FIGURES Page Figure 1.
    [Show full text]